Pi-tricyclene derivatives and process for preparing pi-tricyclene derivatives

ABSTRACT

A process for the preparation of a mixture of compounds of the structure ##SPC1## 
     Is disclosed whereby a Pi-halotricyclene having the structure ##SPC2## 
     Where Y is chloro, bromo or iodo is reacted with an alkali metal cyanide to prepare the corresponding nitrile; the nitrile is reacted with diisobutylaluminum hyhdride to prepare the corresponding aldehyde, a nortricycloekasantalal which is then condensed with butanone to prepare the above mentioned mixture of compounds. Also claimed are the product ketones which are useful for altering the aroma of consumable products including perfumes, perfume compositions and perfumed articles.

BACKGROUND OF THE INVENTION

East Indian sandalwood oil has heretofore been available only from 60-80 year old East Indian sandalwood trees. This oil and various individual components of the oil are highly valued perfume bases and are used in large quantities by the perfume industry. The oil, however, is expensive and is in limited, and sometimes sporadic, supply. For this reason, a continuous effort has been made to synthesize the various components of sandalwood oil or similar synthetic materials which possess the several desirable nuances (e.g., woody, oily, green) of sandalwood oil.

The processes presented herein for preparing various sandalwood aroma components represent a portion of an extensive effort to obtain various components of sandalwood oil as well as substitutes therefor. Other processes and components related to the synthesis of sandalwood oil aroma-like components are described in the following publications:

I. U.S. Pat. No. 3,478,114 issued on Nov. 11, 1969, Title: PROCESS FOR MAKING ALPHA-SANTALOL

Covers the process: ##SPC3##

II. U.S. Pat. No. 3,662,007 issued on May 9, 1972, Title: PROCESS FOR PREPARING DIHYDRO-BETASANTALOL FROM 3-ENDO-METHYL-3-EXO (4'-METHYL-5'-HYDROXYPHENYL) NORCAMPHOR

Covers the process for preparing dihydrobeta-santalol from 3-endo-methyl-3-exo (4'-methyl-5'-hydroxypentyl) norcamphor comprising the steps of (1) reacting 1-endo methyl-3-exo(4'-methyl-5'-hydroxypentyl) norcamphor with either boric acid or boric anhydride to obtain the borate ester of 3-endo-methyl-3-exo(4'-methyl-5'-hydroxypentyl) norcamphor, and (2) reacting the borate ester reaction product of Step (1) with a phosphorous compound such as methyltriphenylphosphonium bromide and subsequently hydrolyzing the reaction product with water to obtain dihydro-beta-santalol.

iii. U.S. Pat. No. 3,662,008 issued on May 9, 1972, Title: PROCESS FOR PREPARING BETA-SANTALOL FROM 3-METHYLNORCAMPHOR

Covers the process for preparing beta-santalol from 3-methylnorcamphor comprising the steps of (1) alkylating 3-methylnorcamphor in strong base with an allyl halide; (2) reacting the reaction product of Step (1) with a methylmetallic compound, such as methyllithium, followed by hydrolysis; (3) brominating the reaction product of Step (2); (4) dehydrobrominating the reaction product of Step (3) with a base, such as sodium amide; (5) dehydrating the reaction product of Step (4) with a dehydrating agent, such as thionyl chloride; (6) reacting the reaction product of Step (5) with a compound, such as di(sec.iso-amyl)borane followed by an oxidation; (7) reacting the reaction product of Step (6) with (carbethoxyethylidene) triphenylphosphorane; and (8) reducing the reaction product of Step (7) with a reducing agent such as lithium aluminum hydride, to obtain beta-santalol.

iv. U.S. Pat No. 3,673,261 issued on June 27, 1972, Title: PERFUME COMPOUNDS AND PROCESS FOR PREPARING SAME

Covers the use in perfumery compounds having the following structures: ##SPC4##

v. U.S. Pat. No. 3,673,263 issued on June 27, 1972, Title: DIHYDRO-BETA-SANTALOL AND PROCESS FOR PREPARING DIHYDRO-BETA-SANTALOL FROM 3-ENDO-METHYL-3-EXO(4'-METHYL-5'-HYDROXYPENTYL) NORCAMPHOR

vi. U.S. Pat. No. 3,673,266 issued on June 27, 1972, Title: PROCESS FOR PREPARING DIHYDRO-BETA-SANTALOL FROM 3-ENDO-METHYL-3-EXO (4'-METHYL-5'-HYDROXYPENTYL) NORCAMPHOR

vii. Corey, et al., J. Am. Chem. Soc. 79, 5773 (1957), Title: THE SYNTHESIS OF ALPHA-SANTALENE AND OF TRANS-Δ11,12-ISO-ALPHASANTALENE

Describes the following process sequence: ##SPC5##

However, none of the above processes explicitly or implicitly represent what are today deemed to be economically feasible techniques for providing the important and novel sandalwood aroma components having the generic structure: ##SPC6##

wherein Z is a moiety selected from the group consisting of: ##SPC7##

Furthermore, the structures of sandalwood aroma components set forth in the above-mentioned prior art are chemically different in kind from the novel compounds of this invention which have the generic structure: ##SPC8##

wherein X is a moiety selected from the group consisting of: ##SPC9##

and wherein R₁ and R₂ are each selected from the group consisting of hydrogen and methyl, at least one of R₁ and R₂ being hydrogen. The novel compounds of this invention have properties considered to be unobvious and advantageous over the compounds set forth in the aforecited prior art.

THE INVENTION

It has now been determined that several π-tricyclene derivatives are capable of imparting notes important to sandalwood fragrance to various consumable materials. Briefly, our invention contemplates altering the fragrance of such consumable materials as perfumes, perfume formulations and perfumed articles by adding thereto a small but effective amount of at least one of the novel π-tricyclene derivatives having a generic structure: ##SPC10##

wherein X is a moiety selected from the group consisting of: ##SPC11##

and wherein R₁ and R₂ are each selected from the group consisting of hydrogen and methyl, at least one of R₁ or R₂ being hydrogen.

Examples of π-tricyclene derivatives useful in the practice of our invention and particularly useful in contributing key notes to sandalwood aromas are as follows:Compound Name Structure Olfactory Properties__________________________________________________________________________5-(2,3-dimethyl- Sweet, woody, oily,tricyclo(2.2.1.0²,6) sweaty, sandalwoodhept-3-yl)3-penten-2- aroma with "sexy-one woody", amber green and orrisy nuances.ortricyclene-9-butenoneor1,7-dimethyl-7-(1-pent-2-en-4-onyl) nortricyclene5-(2,3-dimethyl Green, sweet, woodytricyclo(2.2.1.0²,6) (sandal) aroma.hept-3-yl)3-pentyn-2-oneortricyclene-9-butynoneor1,7-dimethyl-7-(1-pent-2-yn-4-onyl) nortricyclene5-(2,3-dimethyl Green, pumkin-like,tricyclo(2.2.1.0²,6) sandalwood-oilyhept-3-yl)3-pentan- aroma.2-oneortricyclene-9-butanoneor1,7-dimethyl-7-(1-pentan-4-onyl)nortricyclene__________________________________________________________________________

In addition, the following π-tricyclene derivative, also contemplated within the scope of our invention is a valuable reaction intermedate useful for preparing other π-tricyclene derivatives useful for their olfactory properties in perfume compositions and perfumed articles:

    Name of Compound                                                                            Structure                                                         __________________________________________________________________________     5-(2,3-dimethyl tricyclo                                                       (2.2.1.0.sup.2,6)hept-3-yl)                                                    3-pentyn-2-ol                                                                  or                                                                             tricyclene-9-butynol                                                           or                                                                             1,7-dimethyl-1(4'-hydroxy-                                                     pent-2-ynyl) nortricyclene                                                     __________________________________________________________________________

One of the novel processes of our invention capable of yielding compound I, above, is a process for preparing a novel genus for tricyclic ketones having the structure: ##SPC12##

comprising the steps of:

i. Reacting a π-halotricyclene having the structure: ##SPC13##

with an alkali metal cyanide in the presence of an inert solvent thereby forming a nitrile having the structure: ##SPC14##

ii. Reacting the thus formed nitrile with diisobutyl aluminum hydride thus forming a nortricycloekasantalal having the structure: ##SPC15##

iii. Reacting the thus formed nortricycloekasantalal with a ketone having the structure: ##SPC16##

in the presence of a base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides thus forming a tricyclic-alpha,beta-ketone having the structure: ##SPC17##

wherein Y is halogen selected from the group consisting of bromo, chloro and iodol; R₃ is selected from the group consisting of hydrogen and methyl; and wherein R₁ and R₂ are each selected from the group consisting of hydrogen and methyl, provided that at least one of R₁ or R₂ is hydrogen.

This process may optionally include the additional step (iii) of reacting with hydrogen, in the presence of a hydrogenation catalyst, the compound having the structure: ##SPC18##

thereby forming a compound having the structure: ##SPC19##

wherein R₁ and R₂ are each selected from the group consisting of hydrogen and methyl provided that at least one of R₁ or R₂ is hydrogen, in the event that it is desired to prepare compounds such as III, above.

The preparation of π-cyanotricyclene is carried out by reacting an alkali metal cyanide with a π-halo tricyclene having the generic formula: ##SPC20##

wherein Y is a halogen selected from the group consisting of chloro, bromo and iodo. Examples of alkali metal cyanide useful in the reaction are sodium cyanide and potassium cyanide. The reaction is carried out in an inert solvent such as dimethyl sulfoxide at a temperature in the range of from 80°C up to 100°C; preferably 90°C. The mole ratio of alkali metal cyanide to π-halo tricyclene is from 10:1 up to 20:1 with a mole ratio of 15:1 being preferred.

The formation of nortricycloekasantalal is carried out by means of reduction of π-cyanotricyclene using such reducing reagents as diisobutyl aluminum hydride preferably premixed with inert solvent such as hexane. The reaction is carried out in an inert solvent such as hexane or cyclohexane in order to facilitate control of the reaction. The reaction temperature is preferably in the range of from about 40°C up to 80°C with a temperature of about 55°C being preferred. The mole ratio of reduction reagent: π-cyanotricyclene is about 1:1 with the reduction reagent being in slight excess.

The genus of compounds having the structure: ##SPC21##

is prepared by reacting the nortricycloekasantalal with a ketone having the structure: ##SPC22##

wherein R₁, R₂ and R₃ are each hydrogen or methyl with the proviso that at least one of R₁ or R₂ be hydrogen. Where R₃ is hydrogen, both R₁ and R₂ are hydrogen as is the case when the ketone used is acetone. When R₃ is methyl, a mixture of two compounds is produced:one where R₁ is methyl and the other where R₂ is methyl. This mixture can be easily separated by means of fractional distillation, thereby creating two sandalwood oil aroma-imparting components. The reaction is a standard "Aldol Condensation" type reaction which is carried out in the presence of a base which is either an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide or an alkaline earth metal hydroxide such as barium hydroxide or calcium hydroxide. A type of apparatus useful for carrying out the reaction when using an alkaline earth metal hydroxide is a "Soxhlet" apparatus; since the alkaline earth metal hydroxide is only very slightly soluble in the reaction medium.

The temperature of Aldol Condensation reaction is preferably in the range of from 25°C up to 50°C with a temperature of about 35°C being preferred. The mole ratio of ketone:nortricycloekasantalal is preferably in the range of from 5:1 up to 15:1 with a ratio of about 7:1 being preferred. The quantity of base used in the reaction is preferably about 10% of the weight of ketone used; but quantities of base which are as low as 5% of the weight of ketone or as high as 20% of the weight of ketone may be used without creating an adverse effect on the yield of product. Quantities of base lower than 5% by weight of ketone will cause the time of reaction to be unduly lengthened. Quantities of base in excess of 20% will not have any beneficial effect on rate of reaction or yield of product; and will cause an excessive amount of by-products to be formed.

The hydrogenation of the genus of compounds having the structure: ##SPC23##

to form a second genus of compounds represented by the structure: ##SPC24##

is carried out with hydrogen in the presence of a catalyst such as palladium, platinum, nickel or other suitable hydrogenation catalyst. Preferred catalysts are palladium on carbon and Raney nickel.

The reaction temperature may be from 20°-220°C with a temperature range of 20°-50°C being preferred. The reaction is preferably carried out at superatmospheric pressures and pressures in the range of 1-150 atmospheres are suitable. Preferred pressures range from 10-20 atmospheres.

A second of the novel processes of our invention capable of yielding compound II, above, is a process for preparing a tricyclic compound having the structure: ##SPC25##

comprising the steps of:

i. Reacting a π-halo tricyclene having the structure: ##SPC26##

with acetylene lithium having the structure:

    HC.tbd.CLi

thus forming 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene having the structure: ##SPC27##

ii. Reacting the thus formed 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene with R₄ Li to form 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene lithium having the structure: ##SPC28##

iii. Reacting the thus formed 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene lithium with acetaldehyde in the presence of an inert solvent thus forming a tricyclic secondary alpha, beta alkynol having the structure: ##SPC29##

iv. Oxidizing the thus-formed tricyclic secondary alpha, beta alkynol with an alkali metal dichromate in acid solution thus forming a tricyclic alkynyl ketone having the structure: ##SPC30##

wherein Y is bromo, chloro or iodo, and R₄ is selected from the group consisting of phenyl and lower alkyl.

The first step of reacting a π-halo tricyclene having the structure: ##SPC31##

with acetylene lithium having the structure:

    HC.tbd.CLi

to form 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene having the structure: ##SPC32##

is preferably carried out in an inert solvent such as dimethyl sulfoxide. The lithium acetylide reactant is preferably added to the reaction mass in the form of a lithium acetylide - alkylene diamine complex (e.g., ethylene diamine complex) to facilitate control of the reaction. Y is a halogen moiety; either chloro, bromo or iodo. Preferably, the mole ratio of lithium acetylide: halo-tricyclene is about 2:1 but mole ratios of 1.1:1 up to 3:1 are suitable. The temperature of reaction may be in the range of 10°C up to 80°C with room temperature being the preferred reaction temperature. The thus formed 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene is then reacted with R₄ Li to form 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene lithium having the structure: ##SPC33##

where R may be phenyl or alkyl. Thus, for example, suitable R₄ Li compounds are phenyl lithium, n-butyl lithium or t-butyl lithium.

The reaction is carried out in an inert solvent such as tetrahydrofuran. The preferred concentration range of reactant in solvent is from 0.05 up to 0.5 molar. The operable reaction temperature range is from 0°C up to 50°C with room temperature being preferred and most convenient.

The thus-formed 1,7-dimethyl-(1-prop-2-ynyl) nortricyclene lithium is reacted with acetaldehyde in the presence of an inert solvent such as tetrahydrofuran or benzene or a mixture of these, or toluene thus forming a tricyclic secondary alkynol having the structure: ##SPC34##

This reaction is preferably carried out at atmospheric pressure and at a temperature in the range of 10°C up to 50°C; preferably and conveniently at room temperature.

The oxidation of the tricyclic secondary alkynol to the ketone is most preferably carried out using an alkali metal dichromate or a "chromic acid" oxidizing agent. Other oxidizing agents which may be used in the reaction in place of chromic acid are potassium permanganate, manganese dioxide, oxygen and air. It is most preferable to carry out this oxidation reaction in the presence of a solvent such as toluene although other solvents are also useful, such as pyridine, alpha-picoline, beta-picoline, delta-picoline, piperidine and ethanol amine.

When each of the aforementioned reactions is complete, the reaction mixture may be "worked up" using routine purification procedures including the unit operations of extractions, crystallization, preparative chromatographic techniques, drying and/or distillation.

The π-tricyclene derivatives of our invention having a sweet, woody, oily and green sandalwood-like notes can be used to contribute sandalwood aromas.

Although existant in relatively low proportions in sandalwood oil, compound (I) of our invention is considered to be at least one of the primary "sandalwood" aroma contributors of all of the constituents of sandalwood oil. Indeed, the relative strength of its aroma is several-fold that of any other known aroma contributors heretofore found in sandalwood oil; and this property is unexpected.

As olfactory agents several of the π-tricyclene derivatives of this invention can be formulated into or used as components of a "perfume composition".

The term perfume composition is used herein to mean a mixture of organic compounds, including, for example, alcohols, aldehydes, ketones, nitriles, esters, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note of the "bouquet" or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh smelling materials.

In perfume compositions the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, π-tricyclene derivatives of this invention, can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of the π-tricyclene derivative of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 2 percent of the π-tricyclene derivative of this invention, or even less, can be used to impart a patchouli scent to soaps, cosmetics, and the other products. The amount employed can range up to 50% or higher and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and particular fragrance sought.

The π-tricyclene derivative of this invention can be used alone or in a perfume composition as an olfactory component in detergents and soaps, space odorants and deodorants; perfumes; colognes; toilet waters; bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, and sum screens; powders such as talcs, dusting powders, face powder and the like. When used as an olfactory component of a perfumed article, as little as 0.01 percent of the π-tricyclene derivative will suffice to impart a key part of sandalwood aroma. Generally, no more than 0.5 percent is required.

In addition, the perfume composition can contain a vehicle or carrier for the π-tricyclene derivative alone or with other ingredients. The vehicle can be a liquid such as an alcohol such as ethanol, a glycol such as propylene glycol, or the like. The carrier can be an absorbent solid such as a gum or components for encapsulating the composition.

The following examples are given to illustrate embodiments of the invention as it is presently preferred to practice it. It will be understood that these examples are illustrative, and the invention is not to be considered as restricted thereto except as indicated in the appended claims. It is to be understood that unless otherwise stated all parts, proportions and percentages are by weight.

EXAMPLE I Preparation of π-Cyanotricyclene

Reaction: ##SPC35##

Into a 500 ml 3-neck, round bottom flask equipped with condenser, thermometer, mechanical stirrer, hot water heating bath and N₂ purge is charged 200 cc distilled dimethyl sulfoxide. 21.6 g (0.1 moles) of (-)-π-bromotricyclene is then added into the 500 ml flask containing the 200 ml of dimethyl sulfoxide. While stirring and purging with nitrogen 77.6 g (1.58 moles) of sodium cyanide is then added. Heating by means of the hot water bath to 90°C is then effected and the 90°C temperature is maintained for 22 hours. The reaction mass is then cooled to 40°C (below which temperature it becomes solidified) and 200 ml of water is added thereto. The aqueous phase is then extracted with five 100 ml portions of petroleum ether. The combined petroleum ether extracts are then washed with three 500 ml portions of saturated sodium chloride solution and dried over anhydrous MgSO₄. The dried extract is filtered and the solvents are evaporated yielding 21.2 g of crude product.

The crude product is distilled on a 2 inch rush-over column and collected three fractions. While distilling the condenser has to be heated as the pure nitrile solidifies.

    ______________________________________                                         Distillation Data:                                                             Fraction                                                                               Vapor     Liquid    Weight of                                                                              Pressure                                   No.     Temp.     Temp.     Fraction                                           ______________________________________                                         1       30-52°C                                                                           60-65°C                                                                           0.1 g   0.15 mm Hg                                 2        55        70       1.7     0.15                                       3        70        90       9.0     0.10                                       ______________________________________                                    

Nmr, mass spectral and IR analyses confirm that fractions 1 and 2 consist essentially of π-cyanotricyclene having the structure: ##SPC36##

Analyses:

1. Mass spectral analysis in order of decreasing intensity: m/e = 93, 121, 39, 27, 41.

2. The NMR spectrum is illustration in FIG. 1.

3. the IR spectrum is illustrated in FIG. 2.

EXAMPLE II Preparation of Nortricycloekasantalal

Reaction: ##SPC37##

Into a 250 ml 3-neck, round bottom flask equipped with thermometer, condenser, mechanical stirrer, heating mantle, cooling bath (and mantle) and dropping funnel containing 75 ml hexane is charged 9 g (0.055 moles) of π-cyanotricyclene having the structure: ##SPC38##

prepared according to Example I. While stirring and purging with N₂ slowly added 45 g (0.06 moles) diisobutyl aluminum hydride ("Dibal-H") (20% in hexane) over a period of one-half hours. The reaction temperature rises to 20°C and is heated to 55°C and maintained at that temperature for 4 hours. The reaction mixture is cooled to 5°C and 60 g of diethyl ether containing 0.5 ml of water is added slowly, followed by addition of 75 ml of 10% sulfuric acid. The upper organic phase is separated and washed with 15 ml of NaHCO₃ solution (saturated) and then with three 20 ml portions of saturated NaCl solution. The organic phase is then dried over anhydrous MgSO₄ and filtered. The solvent evaporated, yielding 16.2 g of crude aldehyde which is distilled on a 2 inch "rush-over" column and collected in four fractions. (Yield = 99.5%).

    Fraction                                                                              Liquid     Vapor      Pressure                                                                              Weight of                                  No.    Temperature                                                                               Temperature                                                                               (mm Hg)                                                                               Fraction                                   ______________________________________                                         1       45-48°C                                                                            30-35°C                                                                           0.30   0.6 g                                      2      51         43         0.20   3.3                                        3      65         41         0.15   4.6                                        4      85         46         0.15   0.8                                        ______________________________________                                    

Nmr, mass spectral and IR analyses confirm that fractions 2 and 3 consist essentially of nortricycloekasantalal having the structure: ##SPC39##

Analyses:

1. Mass spectral anslysis (in order of decreasing intensity): m/e = 93/91, 105, 79, 120

2. The NMR spectrum is illustrated in FIG. 3.

3. the IR spectrum is illustrated in FIG. 4.

EXAMPLE III Preparation of 1,7-Dimethyl-7-(1-pent-2-en-4-onyl) Nortricyclene

Reaction: ##SPC40##

Into a 100 ml, 3-neck round bottom flask equipped with magnetic stirrer, thermometer and a heating mantle is placed 6 g (0.037 moles) of nortricycloekasantalal produced according to the process of Example III. A cold solution of 12.0 m. (0.23 moles) of acetone containing 1.2 g of NaOH and 3 ml of water is then added to the nortricycloekasantalal. The reaction mass is heated to 35°C and maintained at that temperature for 7 hours. The mass is then cooled and neutralized with 25 ml of aqueous HCl. The solvents are evaporated using a "roto vap" at about 70°C. The salts are then dissolved with water and the aqueous phase is extracted with five 30 ml portions of diethyl ether. The resulting ethereal solution is washed with three 20 ml portions of saturated NaCl solution, dried over anhydrous MgSO₄ and filtered. The solvents are evaporated yielding 7.2 g of crude product. The crude product is distilled on a 2 inch rush-over column (yield: 80%) yielding the following fractions:

    Fraction                                                                              Liquid     Vapor      Pressure                                                                              Weight of                                  No.    Temperature                                                                               Temperature                                                                               (mm Hg)                                                                               Fraction                                   ______________________________________                                         1       60-116°C                                                                          25-85°C                                                                            0.2-0.3                                                                               --                                         2      119         93        0.2     1.2 g                                     3      140         96        0.2    2.9                                        4      180        105        0.2    0.7                                        ______________________________________                                    

NMR, mass spectral and IR analyses confirm that fractions 2-4 consist essentially of 1,7-dimethyl-7 (1-pent-2-en-4-onyl) nortricyclene having the structure: ##SPC41##

Analyses:

1. Mass spectral analysis (in order of decreasing intensity): m/e = 121, 93, 43, 79, 91, 41

2. The NMR spectrum is illustrated in FIG. 5.

3. the IR spectrum is illustrated in FIG. 6.

4. the NMR analysis is as follows:

    Peak                 Interpretation                                            ______________________________________                                         0.86 ppm      (s)        CH.sub.3 --C--                                        1.06          (s)        CH.sub.3 --C--                                        1.72-0.92                methylene and methine                                                          protons                                                                        O                                                                              ∥                                            2.10          (d)        CH.sub.2 --C=C--C                                                              O                                                                              ∥                                            2.28          (s)        CH.sub.3 --C--                                                                 O                                                                              ∥                                            6.08                     --C=C--C                                                                       H                                                                              |                                            6.95-6.6                 --C=C--C--                                                                     H∥                                                                    O                                                     ______________________________________                                    

5. the infrared analysis is as follows:

855 cm⁻ ¹

985

1088

1160

1190

1260

1370

1440

1460

1640

1675

2850

2950

EXAMPLE IV Preparation of 1,7-Dimethyl-7-(1-prop-2-ynyl) Nortricyclene

Reaction: ##SPC42##

Into a 500 ml 3-neck, round bottom flask equipped with condenser, mechanical stirrer, a thermometer and N₂ purge is placed 240 ml dimethyl sulfoxide. While stirring and purging with N₂ 48 g (0.48 moles) of lithium acetylide-ethylene diamine complex is added to the dimethyl sulfoxide. 38 g (0.24 moles) of (-)-π-bromotricyclene is then added and the reaction mass is stirred for 70 hours at room temperature. The reaction mass is then slowly added to 1600 ml of saturated ammonium chloride solution and extracted with six 200 ml portions of n-hexane. The hexane extracts are combined, washed with five 100 ml portions of saturated NaCl solution and dried over anhydrous MgSO₄. The resulting hexane solution is filtered and the solvent evaporated to obtain 36.5 g of crude product. The crude product is distilled using a 2 inches "splash column" and collected in three fractions as follows:

    Fraction                                                                              Weight of Liquid     Vapor                                              No.    Fraction  Temperature                                                                               Temperature                                                                             Pressure                                  ______________________________________                                         1      2.3       39-45°C                                                                             26-31°C                                                                         0.3 mm Hg                                 2      11.8       60        34       0.2                                       3      4.3       100        35       0.3                                       ______________________________________                                    

Yield: 47%

Nmr, mass spectral and IR analyses confirm that fractions 1-3 consist essentially of 1,7-dimethyl-7(1-prop-2-ynyl) nortricyclene having the structure: ##SPC43##

EXAMPLE V Preparation of 1,7-Dimethyl-7-(4'-hydroxy)pent-2-ynyl) Nortricyclene

Reaction: ##SPC44##

Into a 3 liter round bottom flask equipped with mechanical stirrer, thermometer, condenser, addition funnel, a cooling bath and N₂ inlet is placed 350 ml distilled tetrahydrofuran. 9.0 g (0.055 moles) of 1,7-dimethyl-7-(1-prop-2-ynyl) nortricyclene prepared according to Example IV is then added to the tetrahydrofuran. The resulting mass is cooled to 0°-5°C and, while stirring and purging with N₂, 29 ml of a 2M phenyl lithium solution in benzene is added. The reaction mass is then stirred for 45 minutes and 3 g of acetaldehyde in 25 ml of tetrahydrofuran is added slowly. The reaction mass is then stirred at room temperature for a period of 16 hours. 100 ml of saturated NH₄ Cl solution is then added and tetrahydrofuran is removed on a flash evaporator under reduced pressure and elevated temperature (50°C). To the residue 100 ml of saturated Nacl solution is added. The residue is then extracted with five 100 ml portions of diethyl ether. The combined ether solution is then washed with three 20 ml portions of saturated NaCl solution, dried over anhydrous MgSO₄ and filtered. The solvent is evaporated yielding 17 g of crude material.

The 17 g of crude product is then added to a chromatographic column containing 200 g of 5% deactivated silicic acid. The following table sets forth the various fractions removed from the column with the particular solvents used:

                                 Weight                                            Fraction No.                                                                              Solvent           of Fraction                                       ______________________________________                                         1          250 ml of 2% diethyl                                                                             7      g                                                     ether in isopentane                                                 2          250 ml of 5% diethyl                                                                             2.5    g                                                     ether in isopentane                                                 3          250 ml of 10% diethyl                                                                            0.3    g                                                     ether in isopentane                                                 4          250 ml of 15% diethyl                                                                            2.0    g                                                     ether in isopentane                                                 5          250 ml of 20% diethyl                                                                            0.9    g                                                     ether in isopentane                                                 6          250 ml of diethyl 0.8    g                                                     ether                                                               ______________________________________                                    

Fraction No. 4 weighing 2.0 g is analyzed using GLC apparatus (conditions: 5% Carbowax 20M column; 20 feet × 1/4 inch). Peak 5 is determined by IR, NMR and mass spectral analyses to be a compound having the structure: ##SPC45##

Fraction No. 4 is dissolved in 40 ml diethyl ether and washed with three 5 ml portions of 5% sodium hydroxide in order to remove the phenol. It is then washed with three 25 ml portions of saturated sodium chloride solution, dried over anhydrous magnesium sulfate and filtered. The solvent is evaporated yielding 1.5 g of crude product.

Analysis:

1. Mass spectral analysis (Parent Peak, then in order of decreasing intensity): m/e = 204(M⁺); 41, 55, 39, 70, 93, 43, 121.

2. the NMR spectrum is illustrated in FIG. 7.

3. the IR spectrum is illustrated in FIG. 8.

4. the NMR analysis is as follows:Peak Interpretation______________________________________0.94 (s) CH₃ --C--1.02 (s) CH₃ --C-- H1.44 (d) CH₃ --C--C-- | O1.70-0.84 methylene and methine protons2.06 --CH₂ --C=C--4.6 C=C--C--O-- H______________________________________

5. the infrared analysis is as follows:

820 cm⁻ ¹

855

892

1005

1075

1160

1300

1317

1380

1460

2990

3310

EXAMPLE VI Preparation of 1,7-Dimethyl-7-(1-pent-2-yn-4-onyl) Nortricyclene

Reaction: ##SPC46##

Procedure:

To a 100 ml 3-neck, round bottom flask equipped with stirrer, thermometer and N₂ inlet is added 30 ml of toluene and 1.8 g of the crude material, fraction 4, containing 1,7-dimethyl-7-(1-(4'-hydroxy)pent-2-ynyl) nortricyclene produced according to Example V. While stirring the mixture is cooled to 0°-5°C. A mixture of 1.5 g of Na₂ Cr₂ O₇ in 4 ml of water and 1.5 g of conc. H₂ SO₄ is then added, and the reaction mass is stirred for a period of 3 hours. The resulting organic layer is separated and washed with two 25 ml portions of saturated sodium carbonate solution. The organic phase is then washed with three 20 ml portions of saturated NaCl solution, dried over anhydrous MgSO₄ and filtered. The solvent is evaporated yielding crude product weighing about 1.5 g.

The 1.5 g of crude product is placed in a chromatographic column containing 75 g of 5% deactivated silicic acid. The following table sets forth the various fractions removed from the column giving the particular solvents used for each fraction:

    Fraction No.    Solvent                                                        ______________________________________                                         1               100 ml of 2% diethyl ether                                                     in isopentane                                                  2               100 ml of 2% diethyl ether                                                     in isopentane                                                  3               100 ml of 2% diethyl ether                                                     in isopentane                                                  4               100 ml of 2% diethyl ether                                                     in isopentane                                                  5               100 ml of 4% diethyl                                                           ether in isopentane                                            6               100 ml of 4% diethyl                                                           ether in isopentane                                            7               100 ml of 4% diethyl                                                           ether in isopentane                                            8               100 ml of 4% diethyl                                                           ether in isopentane                                            9               100 ml of 4% diethyl                                                           ether in isopentane                                            10              100 ml of 4% diethyl                                                           ether in isopentane                                            11              100 ml of 4% diethyl                                                           ether in isopentane                                            12              100 ml of 4% diethyl                                                           ether in isopentane                                            13              100 ml of 6% diethyl                                                           ether in isopentane                                            14              100 ml of 6% diethyl                                                           ether in isopentane                                            15              100 ml of 6% diethyl                                                           ether in isopentane                                            16              100 ml of 6% diethyl                                                           ether in isopentane                                            17              500 ml of 8% diethyl                                                           ether in isopentane                                            18              500 ml of 10% diethyl                                                          ether in isopentane                                            ______________________________________                                    

Fractions Nos. 10-12 are combined and evaporated. The components are then trapped using GLC apparatus (conditions: 5% Carbowax 20M column; 20 feet × 1/4 inch). Peak No. 4 consists essentially of the compound having the structure: ##SPC47##

as confirmed by NMR, IR and mass spectral analyses. It has a green, sweet, sandalwood aroma.

Analysis:

1. Mass spectral analysis (parent peak, then in order of decreasing intensity: m/e = 202(M⁺); 93, 43, 41, 39, 121, 55.

2. the IR spectrum is illustrated in FIG. 9.

EXAMPLE VII Preparation of 1,7-Dimethyl-7-(1-pentan-4-onyl) Nortricyclene

Reaction: ##SPC48##

A Parr (2 L Bomb) pressure reaction apparatus equipped with a stirrer and connected to a hydrogen cylinder is charged with 1,7-dimethyl-7-(1-pent-2-en-4-onyl) nortricyclene prepared according to the procedure of Example III 500 g, isopropyl alcohol 250 g, Raney Nickel 25 g and the hydrogenation is carried out at 25°C under a pressure of 250 psi for 2 hours. The progress of the reaction is monitored by observing the disappearance of IR bands at 6.1 and 10.2 u and the shifting of the carbonyl absorption band from 5.9 to 5.8 u. The reaction mixture is filtered through Celite and the solvent is evaporated in a Rinco flask evaporator under house vacuum to obtain 490 g of crude material (yield = 98%).

NMR, IR and mass spectral analysis confirm the structure of the reaction product as being: ##SPC49##

This material has a green, pumpkin like, sandalwood-oily-like aroma.

Analyses:

1. Mass spectral analysis (in decreasing order of intensity): m/e = 121, 93, 206 (Molecular ion), 43, 107.

2. The NMR spectrum is illustrated in FIG. 10.

3. the IR spectrum is illustrated in FIG. 11.

4. the NMR analysis is as follows:

    Peak             Interpretation                                                ______________________________________                                         0.84 ppm    (s)      CH.sub.3 --C--                                                                                6H                                         1.50        (s)      CH.sub.3 --C--                                            1.76-1.10   (m)      Methylene and 11H                                                              methine protons                                           2.14        (s)      CH.sub.3 --C=O                                                                                3H                                         2.41        (t)      --CH.sub.2 --C=O                                          ______________________________________                                    

5. the infrared analysis is as follows:

855 cm⁻ ¹

1165

1370

1420

1460

1725

2900

2950

EXAMPLE VIII Separation of Sandalwood Oil Components

200 g of sandalwood oil is admixed with 2 liters of diethyl ether. The resulting mixture is washed with three 50 ml portions of 10% sodium carbonate solution. The washings are combined and they are washed with five 50 ml portions of diethyl ether. The resulting ether washings are combined with the original washed ether solution and this combined diethyl ether solution is then washed with three 50 ml portions of 5% aqueous sodium hydroxide. The sodium hydroxide washings are re-extracted with five 50 ml portions of diethyl ether and these ether extracts are combined with the original ether solution and the combined ether solution is then extracted with three 50 ml portions of 4% hydrochloric acid. The extracted ether solution is then washed with 100 ml saturated sodium chloride solution followed by four 50 ml portions of water (until the water washing no longer shows an acid pH). The ether solution is then dried over anhydrous magnesium sulfate filtered and evaporated to yield 197.8 g of crude product.

a. 140 g of the material is then distilled on a spinning band column operating at a reflux ratio of 100:1 and 6 fractions are collected.

    Fraction                                                                              Vapor      Liquid     Pressure                                                                              Weight of                                  No.    Temperature                                                                               Temperature                                                                               (mm Hg)                                                                               Fraction                                   ______________________________________                                         1       70-72°C                                                                           152-156°C                                                                           0.40  1.8                                        2      74         156         0.45  1.9                                        3      80         160        0.6    1.8                                        4      92         160        0.6    1.9                                        5      93         161        0.6    2.6                                        6      90         161        0.6    2.3                                        ______________________________________                                    

b. 55 g of the above material are also distilled on a spinning band column yielding 5 fractions as follows:

    Fraction                                                                              Vapor      Liquid     Pressure                                                                              Weight of                                  No.    Temperature                                                                               Temperature                                                                               (mm Hg)                                                                               Fraction                                   ______________________________________                                         1      70-74°C                                                                            158-160°C                                                                          0.5-0.6                                                                               2.1                                        2       78        160        0.4    1.7                                        3       98        160        0.6    1.7                                        4      103        160        0.6    1.6                                        5      105        158        0.6    1.3                                        ______________________________________                                    

The combined distillates of distillation operations (a) and (b), supra, are placed in a chromatographic column containing 400 g of 5% deactivated silicic acid. Initially, two fractions are removed:

i. The first fraction contains hydrocarbon and is removed with 1.5 liters of isopentane;

ii. The second fraction contains oxygenated material and is removed with 1.5 liters of diethyl ether.

The oxygenated material is then placed in a Carbowax column containing 130 g of 5% deactivated silicic acid. The following table sets forth the various fractions removed from the column giving the particular solvents used for each fraction:

    Fraction No.    Solvent                                                        ______________________________________                                         1               350 ml of 1% diethyl                                                           ether in isopentane                                            2               150 ml of 1% diethyl                                                           ether in isopentane                                            3               100 ml of 2% diethyl                                                           ether in isopentane                                            4               100 ml of 2% diethyl                                                           ether in isopentane                                            5               100 ml of 2% diethyl                                                           ether in isopentane                                            6               100 ml of 2% diethyl                                                           ether in isopentane                                            7               50 ml of 2% diethyl                                                            ether in isopentane                                            8               50 ml of 2% diethyl                                                            ether in isopentane                                            9               50 ml of 2% diethyl                                                            ether in isopentane                                            10              50 ml of 2% diethyl                                                            ether in isopentane                                            11              25 ml of 2% diethyl                                                            ether in isopentane                                            12              25 ml of 2% diethyl                                                            ether in isopentane                                            13              25 ml of 2% diethyl                                                            ether in isopentane                                            14              25 ml of 2% diethyl                                                            ether in isopentane                                            15              25 ml of 2% diethyl                                                            ether in isopentane                                            16              25 ml of 2% diethyl                                                            ether in isopentane                                            17              25 ml of 2% diethyl                                                            ether in isopentane                                            18              25 ml of 2% diethyl                                                            ether in isopentane                                            19              25 ml of 2% diethyl                                                            ether in isopentane                                            20              25 ml of 2% diethyl                                                            ether in isopentane                                            21              25 ml of 2% diethyl                                                            ether in isopentane                                            22              25 ml of 2% diethyl                                                            ether in isopentane                                            23              25 ml of 2% diethyl                                                            ether in isopentane                                            24              25 ml of 2% diethyl                                                            ether in isopentane                                            25              25 ml of 2% diethyl                                                            ether in isopentane                                            26              25 ml of 2% diethyl                                                            ether in isopentane                                            27              25 ml of 2% diethyl                                                            ether in isopentane                                            28              25 ml of 2% diethyl                                                            ether in isopentane                                            29              25 ml of 3% diethyl                                                            ether in isopentane                                            30              25 ml of 3% diethyl                                                            ether in isopentane                                            31              25 ml of 3% diethyl                                                            ether in isopentane                                            32              25 ml of 3% diethyl                                                            ether in isopentane                                            33              25 ml of 3% diethyl                                                            ether in isopentane                                            34              25 ml of 3% diethyl                                                            ether in isopentane                                            35              25 ml of 3% diethyl                                                            ether in isopentane                                            36              25 ml of 3% diethyl                                                            ether in isopentane                                            37              25 ml of 3% diethyl                                                            ether in isopentane                                            38              25 ml of 3% diethyl                                                            ether in isopentane                                            39              25 ml of 3% diethyl                                                            ether in isopentane                                            40              25 ml of 3% diethyl                                                            ether in isopentane                                            41              25 ml of 3% diethyl                                                            ether in isopentane                                            42              25 ml of 4% diethyl                                                            ether in isopentane                                            43              25 ml of 4% diethyl                                                            ether in isopentane                                            44              25 ml of 4% diethyl                                                            ether in isopentane                                            45              25 ml of 4% diethyl                                                            ether in isopentane                                            46              25 ml of 4% diethyl                                                            ether in isopentane                                            47              25 ml of 4% diethyl                                                            ether in isopentane                                            48              25 ml of 4% diethyl                                                            ether in isopentane                                            49              25 ml of 4% diethyl                                                            ether in isopentane                                            50              25 ml of 4% diethyl                                                            ether in isopentane                                            51              25 ml of 4% diethyl                                                            ether in isopentane                                            52              25 ml of 4% diethyl                                                            ether in isopentane                                            53              25 ml of 4% diethyl                                                            ether in isopentane                                            54              25 ml of 4% diethyl                                                            ether in isopentane                                            55              25 ml of 4% diethyl                                                            ether in isopentane                                            56              25 ml of 4% diethyl                                                            ether in isopentane                                            57              25 ml of 4% diethyl                                                            ether in isopentane                                            58              25 ml of 5% diethyl                                                            ether in isopentane                                            59              25 ml of 5% diethyl                                                            ether in isopentane                                            60              25 ml of 5% diethyl                                                            ether in isopentane                                            61              25 ml of 5% diethyl                                                            ether in isopentane                                            62              25 ml of 5% diethyl                                                            ether in isopentane                                            63              25 ml of 5% diethyl                                                            ether in isopentane                                            64              25 ml of 5% diethyl                                                            ether in isopentane                                            65              25 ml of 5% diethyl                                                            ether in isopentane                                            66              25 ml of 5% diethyl                                                            ether in isopentane                                            67              25 ml of 5% diethyl                                                            ether in isopentane                                            68              25 ml of 5% diethyl                                                            ether in isopentane                                            69              25 ml of 5% diethyl                                                            ether in isopentane                                            70              25 ml of 5% diethyl                                                            ether in isopentane                                            71              25 ml of 5% diethyl                                                            ether in isopentane                                            72              25 ml of 5% diethyl                                                            ether in isopentane                                            73              25 ml of 6% diethyl                                                            ether in isopentane                                            74              25 ml of 6% diethyl                                                            ether in isopentane                                            75              25 ml of 6% diethyl                                                            ether in isopentane                                            76              25 ml of 6% diethyl                                                            ether in isopentane                                            77              25 ml of 6% diethyl                                                            ether in isopentane                                            78              25 ml of 6% diethyl                                                            ether in isopentane                                            79              25 ml of 6% diethyl                                                            ether in isopentane                                            80              25 ml of 6% diethyl                                                            ether in isopentane                                            81              25 ml of 6% diethyl                                                            ether in isopentane                                            82              25 ml of 6% diethyl                                                            ether in isopentane                                            83              25 ml of 6% diethyl                                                            ether in isopentane                                            84              25 ml of 6% diethyl                                                            ether in isopentane                                            85              25 ml of 6% diethyl                                                            ether in isopentane                                            86              25 ml of 6% diethyl                                                            ether in isopentane                                            87              25 ml of 6% diethyl                                                            ether in isopentane                                            88              25 ml of 6% diethyl                                                            ether in isopentane                                            89              25 ml of 6% diethyl                                                            ether in isopentane                                            90              25 ml of 6% diethyl                                                            ether in isopentane                                            91              25 ml of 6% diethyl                                                            ether in isopentane                                            92              25 ml of 7% diethyl                                                            ether in isopentane                                            93              25 ml of 7% diethyl                                                            ether in isopentane                                            94              25 ml of 7% diethyl                                                            ether in isopentane                                            95              25 ml of 7% diethyl                                                            ether in isopentane                                            96              25 ml of 7% diethyl                                                            ether in isopentane                                            97              25 ml of 7% diethyl                                                            ether in isopentane                                            98              25 ml of 7% diethyl                                                            ether in isopentane                                            99              25 ml of 7% diethyl                                                            ether in isopentane                                            100             25 ml of 7% diethyl                                                            ether in isopentane                                            101             25 ml of 7% diethyl                                                            ether in isopentane                                            102             25 ml of 7% diethyl                                                            ether in isopentane                                            103             25 ml of 7% diethyl                                                            ether in isopentane                                            104             25 ml of 7% diethyl                                                            ether in isopentane                                            105             25 ml of 7% diethyl                                                            ether in isopentane                                            106             25 ml of 10% diethyl                                                           ether in isopentane                                            107             25 ml of 10% diethyl                                                           ether in isopentane                                            108             25 ml of 10% diethyl                                                           ether in isopentane                                            109             25 ml of 10% diethyl                                                           ether in isopentane                                            110             25 ml of 10% diethyl                                                           ether in isopentane                                            111             25 ml of 10% diethyl                                                           ether in isopentane                                            112             25 ml of 10% diethyl                                                           ether in isopentane                                            113             25 ml of 10% diethyl                                                           ether in isopentane                                            114             25 ml of 10% diethyl                                                           ether in isopentane                                            115             25 ml of 10% diethyl                                                           ether in isopentane                                            116             25 ml of 10% diethyl                                                           ether in isopentane                                            117             25 ml of 10% diethyl                                                           ether in isopentane                                            118             25 ml of 10% diethyl                                                           ether in isopentane                                            119             25 ml of 10% diethyl                                                           ether in isopentane                                            120             25 ml of 15% diethyl                                                           ether in isopentane                                            121             25 ml of 15% diethyl                                                           ether in isopentane                                            122             25 ml of 15% diethyl                                                           ether in isopentane                                            123             25 ml of 15% diethyl                                                           ether in isopentane                                            124             25 ml of 15% diethyl                                                           ether in isopentane                                            125             25 ml of 15% diethyl                                                           ether in isopentane                                            126             25 ml of 15% diethyl                                                           ether in isopentane                                            127             25 ml of 15% diethyl                                                           ether in isopentane                                            128             25 ml of 15% diethyl                                                           ether in isopentane                                            129             25 ml of 15% diethyl                                                           ether in isopentane                                            130             25 ml of 15% diethyl                                                           ether in isopentane                                            131             100 ml of 20% diethyl                                                          ether in isopentane                                            132             100 ml of 20% diethyl                                                          ether in isopentane                                            133             100 ml of 20% diethyl                                                          ether in isopentane                                            134             50 ml of 30% diethyl                                                           ether in isopentane                                            135             500 ml of 40% diethyl                                                          ether in isopentane                                            136             250 ml of 50% diethyl                                                          ether in isopentane                                            137             750 ml of 100% diethyl                                                         ether in isopentane                                            ______________________________________                                    

The solvent is evaporated from fractions 41 and fraction 41 is separated using GLC (conditions: 5% Carbowax 20M column; 20 feet × 1/4 inch) IR, NMR and mass spectral analyses of the compound in GLC peak 7c yields the information that the structure of the compound in Peak 7c is: ##SPC50##

Analysis:

NMR, IR and mass spectral analyses are identical to those of the same compound produced in Example VII. The NMR and IR spectra are illustrated respectively in FIGS. 10 and 11.

The solvent is evaporated from fraction 63 and this material is trapped out using GLC apparatus (conditions: 5% carbowax 20M column; 20 feet × 1/4 inch). Peak 3a is analyzed using IR, NMR and mass spectral analyses and these analyses yield information confirming the structure of the compound of Peak 3a to be: ##SPC51##

Analysis:

NMR, IR and mass spectral analyses are identical to those of the same compound produced in Example III. The NMR and IR spectra are illustrated respectively in FIGS. 5 and 6.

EXAMPLE IX Sandal Perfume Formulation

The following mixture is prepared:

    Ingredients           Parts by Weight                                          ______________________________________                                         1',2',3',4',5',6',7',8'-                                                                             540                                                      octahydro-2',3',8',8'-                                                         tetramethyl-2'-acetonaphthone                                                  isomer mixture produced                                                        according to the process of                                                    Example VII of Application for                                                 U.S. Letters Pat. No.                                                          434,948 filed on January 21,                                                   1974                                                                           Cedrenal - (A tricyclic                                                                              90                                                       sesquiterpinic aldehyde                                                        derived from cedrene, having                                                   the structure:                                                                 produced according to the                                                      process of U.S. Pat.                                                           Application 260,537 filed                                                      on June 7, 1972 (corresponding                                                 to published Dutch Appln.                                                      7,307,849 laid open for                                                        public inspection on December 11,                                              1973)                                                                          Eugenol (1% in ethyl alcohol)                                                                        54                                                       2,5,5-trimethyl acetyl cyclo-                                                                        180                                                      heptane produced according                                                     to Example I of U.S. Pat.                                                      Application 349,180 filed on                                                   April 9, 1973                                                                  Borneol (1% in ethyl alcohol)                                                                        18                                                       Hexahydro-4,7-methanoindane-2-                                                                       18                                                       carboxaldehyde                                                                 Tricyclene-9-butenone having                                                                         100                                                      produced according to Example III                                              ______________________________________                                    

The tricyclene-9-butenone imparts the green, woody, slightly sweaty note of sandal to the formulation.

EXAMPLE X Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 g of the perfume composition set forth in Example IX until a substantially homogeneous composition is obtained. The soap composition manifests a characteristic "sandal cologne" aroma having

EXAMPLE XI Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 g of tricyclene-9-butenone produced according to Example III until a substantially homogeneous composition is obtained. The soap composition manifests a green, woody, sandalwood oil character.

EXAMPLE XII Preparation of a Detergent Composition

A total of 100 g of a detergent powder sold under the trademark "RINSO" are mixed with 0.15 g of a perfume composition containing the mixture obtained in Example IX until a substantially homogeneous composition having a sandal cologne fragrance with green, woody and sweaty notes is obtained.

EXAMPLE XIII Preparation of a Cosmetic Base

A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25 g of the perfume composition of Example IX in a ball mill. A second cosmetic powder is similarly prepared except that the mixture produced in Example IX is replaced with the product produced in Example III. The cosmetic powder containing the material of Example IX has a sandal cologne fragrance with a green, woody, sweaty character. The cosmetic powder produced using this material of Example III also has a sandalwood aroma with sweet, woody, oily, sweaty, amber and orrisey notes.

EXAMPLE XIV Liquid Detergent Containing Tricyclene-9-Butenone

Concentrated liquid detergents with a sandalwood-like odor containing 0.2%, 0.5% and 1.2% of the product produced in accordance with the process of Example III are prepared by adding the appropriate quantity of tricyclene-9-butenone to the liquid detergent known as P-87. The sandalwood aroma of the liquid detergent increases with increasing concentration of the tricyclene-9-butenone of this invention.

EXAMPLE XV Preparation of Cologne and Handkerchief Perfume

The composition of Example IX is incorporated in a cologne having a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume in a concentration of 20% (in 95% ethanol). The use of the composition of Example IX affords a distinct and definite sandal cologne aroma having a warm sandalwood-like character to the handkerchief perfume and to the cologne.

EXAMPLE XVI Cologne and Handkerchief Perfume

The tricyclene-9-butenone produced by the process of Example III is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of 10% (in 95% ethanol). The tricyclene-9-butenone produced in Example III affords a distinct and definite sandalwood aroma with sweet, woody, oily, sweaty, amber and orrisey notes to the handkerchief perfume and to the cologne.

EXAMPLE XVII Sandal Perfume Formulation

The following mixture is prepared:Ingredients Parts by Weight______________________________________1',2',3',4',5',6',7',8'- 540octahydro-2',3',8',8'-tetramethyl-2'-acetonaphthoneisomer mixture produced accordingto the process of Example VII ofApplication for U.S. LettersPat. No. 434,948 filed onJanuary 21, 1974Cedrenal - (A tricyclic 90sesquiterpinic aldehydederived from cedrene, havingthe structure:produced according to theprocess of U.S. Pat.Application 260,537 filed onJune 7, 1972 (correspondingto published Dutch Appln.7,307,849 laid open for publicinspection on December 11, 1973)Eugenol (1% in ethyl alcohol) 542,5,5-trimethyl acetyl cyclo- 180heptane produced according toExample I of U.S. Pat.Application 349,180 filed onApril 9, 1973Borneol (1% in ethyl alcohol) 18Hexahydro-4,7-methanoindane-2- 18carboxaldehydeTricyclene-9-butynone having the 100structure:produced according to Example VI______________________________________

The tricyclene-9-butynone imparts the green, woody, sweet note of sandal to the formulation.

EXAMPLE XVIII Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 g of the perfume composition set forth in Example XVII until a substantially homogeneous composition is obtained. The soap composition manifests a characteristic sandal cologne aroma having green, sweet and woody notes.

EXAMPLE XIX Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 g of tricyclene-9-butynone produced according to Example VI until a substantially homogeneous composition is obtained. The soap composition manifests a sandalwood-like character with green, woody and sweet notes.

EXAMPLE XX Preparation of a Detergent Composition

A total of 100 g of a detergent powder sold under the trademark "RINSO" are mixed with 0.15 g of a perfume composition containing the mixture obtained in Example XVII until a substantially homogeneous composition having a sandal cologne fragrance with green, sweet and woody notes is obtained.

EXAMPLE XXI Preparation of a Cosmetic Base

A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25 g of the perfume composition of Example XVII in a ball mill. A second cosmetic powder is similarly prepared except that the mixture produced in Example XVII is replaced with the product produced in Example VI. The cosmetic powder containing the material of Example XVII has a sandal cologne fragrance with a green, sweet woody character. The cosmetic powder produced using the material of Example VI has a sandalwood-like aroma with green, sweet, woody notes.

EXAMPLE XXII Liquid Detergent Containing Tricyclene-9-Butynone

Concentrated liquid detergents with a sandalwood like odor containing 0.2%, 0.5% and 1.2% of the product produced in accordance with the process of Example VI are prepared by adding the appropriate quantity of tricyclene-9-butynone to the liquid detergent known as P-87. The sandalwood aroma of the liquid detergent increases with increasing concentration of the tricyclene-9-butynone of this invention.

EXAMPLE XXIII Preparation of Cologne and Handkerchief Perfume

The composition of Example XVII is incorporated in a cologne having a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume in a concentration of 20% (in 95% ethanol). The use of the composition of Example XVII affords a distinct and definite sandal cologne aroma having a warm sandalwood-like character to the handkerchief perfume and to the cologne.

EXAMPLE XXIV Cologne and Handkerchief Perfume

The tricyclene-9-butynone produced by the process of Example VI is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of 10% (in 95% ethanol). The tricyclene-9-butynone produced in Example VI affords a distinct and definite sandalwood-like aroma with green, woody and sweet notes to the handkerchief perfume and to the cologne.

EXAMPLE XXV Sandal Perfume Formulation

The following mixture is prepared:Ingredients Parts by Weight______________________________________1',2',3',4',5',6',7',8'- 540octahydro-2',3',8',8'-tetramethyl-2'-acetonaphthoneisomer mixture produced accordingto the process of Example VII ofApplication for U.S. LettersPat. No. 434,948 filed onJanuary 21, 1974Cedrenal - (A tricyclic 90sesquiterpinic aldehydederived from cedrene, havingthe structure:produced according to theprocess of U.S. Pat. Appli-cation 260,537 filed onJune 7, 1972 (corresponding topublished Dutch Appln.7,307,849 laid open for publicinspection on December 11, 1973)Eugenol (1% in ethyl alcohol) 542,5,5-trimethyl acetyl cyclo- 180heptane produced according toExample I of U.S. Pat. Appli-cation 349,180 filed onApril 9, 1973Borneol (1% in ethyl alcohol) 18Hexahydro-4,7-methanoindane-2- 18carboxaldehydeTricyclene-9-butanone having 100the structure:produced according to Example VII______________________________________

The tricyclene-9-butanone imparts the green, pumkin-like and oily notes of sandal to the formulation.

EXAMPLE XXVI Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 g of the perfume composition set forth in Example XXV until a substantially homogeneous composition is obtained. The soap composition manifests a characteristic sandal cologne aroma having green, oily, pumkin-like notes.

EXAMPLE XXVII Preparation of a Soap Composition

A total of 100 g of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 g of tricyclene-9-butanone produced according to the process of Example VII until a substantially homogeneous composition is obtained. The soap composition manifests a sandalwood character with green, pumpkin-like oily notes.

EXAMPLE XXVIII Preparation of a Detergent Composition

A total of 100 g of a detergent powder sold under the trademark "RINSO" are mixed with 0.15 g of a perfume composition containing the mixture obtained in Example XXV until a substantially homogeneous composition having a sandal cologne fragrance with green, pumpkin-like oily notes is obtained.

EXAMPLE XXIX Preparation of a Cosmetic Base

A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25 g of the perfume composition of Example XXV in a ball mill. A second cosmetic powder is similarly prepared except that the mixture produced in Examaple XXV is replaced with the product produced in Example VII. The cosmetic powder containing the material of Example XXV has a sandal cologne fragrance with a green, oily character. The cosmetic powder produced using this material of Example VII has a sandalwood-like aroma with green, pumkin-like, oily notes.

EXAMPLE XXX Liquid Detergent Containing Tricyclene-9-butanone

Concentrated liquid detergents with a sandalwood-like odor containing 0.2%, 0.5% and 1.2% of the product produced in accordance with the process of Example VII, tricyclene-9-butanone, are prepared by adding the appropriate quantity of tricyclene-9-butanone to the liquid detergent known as P-87. The sandalwood aroma of the liquid detergent increases with increasing concentration of the tricyclene-9-butanone of this invention.

EXAMPLE XXXI Preparation of Cologne and Handkerchief Perfume

The composition of Example XXV is incorporated in a cologne having a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume in a concentration of 20% (in 95% ethanol). The use of the composition of Example XXV affords a distinct and definite sandal cologne aroma having a warm sandalwood-like character to the handkerchief perfume and to the cologne.

EXAMPLE XXXII Cologne and Handkerchief Perfume

The tricyclene-9-butanone produced by the process of Example VII is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of 10% (in 95% ethanol). The tricyclene-9-butanone produced in Example VII affords a distinct and definite sandalwood aroma with green, pumpkin-like, sandalwood-oily notes to the handkerchief perfume and to the cologne. 

What is claimed is:
 1. A process for preparing a mixture of tricyclic ketones having the structures: ##SPC52##comprising the steps of: i. Reacting a Pi-halotricyclene having the structure: ##SPC53## with an alkali metal cyanide in the presence of an inert solvent at a temperature in the range of from 80°C up to 100°C, the mole ratio of alkali metal cyanide to pi-halotricyclene being from 10:1 up to 20:1 thereby forming a nitrile having the structure: ##SPC54## ii. Reacting the thus formed nitrile with diisobutyl aluminum hydride in the presence of an inert solvent, at a temperature in the range of from about 40°C up to 80°C, the mole ratio of diisobutyl aluminum hydride:nitrile being about 1:1, thus forming a nortricycloekasantalal having the structure: ##SPC55## iii. Reacting the thus formed nortricycloekasantalal with butanone having the structure: ##SPC56## in the presence of a base selected from the group consisting of an alkali metal hydroxide and an alkaline earth metal hydroxide at a temperature in the range of from 25°C up to 50°C, the mole ratio of butanone:nortricycloekasantalal being in the range of from 5:1 up to 15:1, the weight of butanone as a percentage of reaction mass being from 5% up to 20%, thus forming a tricyclic-alpha, betaunsaturated ketone mixture of compounds which have the structures: ##SPC57## wherein Y is halogen selected from the group consisting of bromo, chloro and iodo.
 2. The process of claim 1 wherein Y is bromo.
 3. The product produced by the process is claim
 1. 4. The product produced by the process of claim
 2. 5. A mixture of compounds having the structures: ##SPC58## 